JP2015232143A - Silane-based aqueous anticorrosive compound - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an aqueous anticorrosive compound based on a bisaminosilane co-condensed product with largely VOC free.SOLUTION: There is provided a composition containing a binder containing one or more kind of co-condensed product based on ω-glycidyloxy alkylalkoxysilane of the formula I: X-Si(R)(OR)(I), where X is 2-(3,4-epoxycyclohexyl)ethyl group or the like, Rand Rare linear having 1 to 4 carbon atoms or the like and x is 0 or 1, and one or more kind of bis(alkoxysilyl alkyl)amine of the general formula II: (OR)Si-A-Si(OR)(II), where a group Ris linear having 1 to 4 carbon atoms or the like, water, alcohol of less than 3 mass% based on the composition, and one or more additive such as granular metal or the like, having pH value in the composition of 1 to 14 and dry residual of the binder of 1 to 50 mass% based on the used binder.

Description

  The present invention relates to novel anticorrosive formulations based on aqueous silane systems as binders, their production process and their use, in particular for protecting metals from corrosion.

  Aqueous silane systems are of increasing interest because they contain little or no organic solvent and are therefore more environmentally friendly. Furthermore, these systems can be used without explosion protection. Stable aqueous silane systems cannot be easily prepared by mixing silane and water because many silanes are insoluble in the aqueous phase and are hydrolyzed and contacted with water. It is because it condenses. Therefore, silane systems with organic solvents and defined amounts of water are usually used in corrosion protection. They can be blended with additives, pigments and fillers to modify the properties of the silane system or improve the corrosion protection.

  The preparation of water-soluble aminopolysiloxanes is described in European Patent (EP) 0 590 270. The aminosilane is mixed with a corresponding amount of water in a 50% alcohol solution and begins to hydrolyse at 60 ° C. These products are still soluble in water. The disadvantage is still the high content of organic solvents and the accompanying low flash point.

  German Offenlegungsschrift (DE) 103 35 178 likewise describes the preparation of a mixture comprising a water-soluble silane system, for example 3-aminopropyltrialkoxysilane and bis (trialkoxysilylpropyl) amine. Have been described. The silane mixture begins to hydrolyze with a defined amount of water. Here again, however, the silane mixture contains 25-99.99% alcohol and is therefore not VOC free.

  US Pat. No. 5,051,129 claims the protection of a patent for an aqueous solution composition comprising a water-soluble aminosilane and an alkyltrialkoxysilane. The production takes place by adding a defined amount of water to the silane mixture, followed by temperature regulation at 60 ° C. The silane mixture thus produced is dissolved in water at a specific ratio and is used for hydrophobizing the surface.

  European patent (EP) 0 716 128 claims protection of water-based organopolysiloxane-containing compositions, methods for their production and use. Mixing water-soluble aminoalkylalkoxysilanes with alkyltrialkoxysilanes and / or dialkyldialkoxysilanes and adding water at a defined pH value results in an organopolysiloxane-containing composition. The resulting hydrolyzed alcohol is removed by distillation. Thus, VOC-free aqueous polysiloxane-containing compositions are obtained, which can be used for hydrophobing surfaces, mineral building materials and further applications.

  International Publication (WO) 2000/39177 describes the use of bissilylaminosilane and / or bissilylpolysulfane in aqueous solution. The silane is mixed with water, alcohol and optionally acetic acid and hydrolyzed for at least 24 hours. Subsequently, it is used on metal.

  US Pat. No. 6,955,728 describes the use of acetoxysilane in combination with other silanes in aqueous solution and on metals. In particular, bis (trialkoxysilylpropyl) amine is also used in combination with acetoxysilane. The stability of the aqueous solution is not stated, or a two-component system that is united for the first time before the use is recommended. The aqueous solution contains the hydrolyzed alcohol at least at any time.

  In WO 2004/076717 bissilylaminosilane is used in aqueous solution in combination with further silanes and metal chelates. The silane is partially hydrolyzed by aging in an aqueous concentrate for at least 2 weeks. Subsequently, the metal chelate is added and further diluted with water. Furthermore, all aqueous formulations still contain alcohol from the hydrolysis. The aqueous system is used for pretreatment of metal surfaces.

  International Publication (WO) 2004/076718 relates to a method of coating a metal surface with an aqueous solution containing a partially hydrolyzed silane, such as bissilylaminosilane, and a partially hydrolyzed fluorine-containing silane. Use of the fluorine-containing silane improves the hydrophobicity and corrosion resistance of the coating system. The hydrolyzed alcohol is not removed from the system.

  US Pat. No. 5,206,285 describes the preparation and use of water-based addition products from epoxysilanes and aminosilanes. The aqueous silane system is not solventless. These are used in metal coatings and are said to improve the corrosion resistance.

  EP 1 760 128 claims protection of aqueous two-component adhesion promoter compositions and patents for their use for adhesion or sealing. The component of the adhesion promoter (Haftvermittler) may contain bissilylaminosilane.

  DE 10 2004 037 045 relates to an aqueous silane nanocomposite produced from glycidyloxypropylalkoxysilane and an aqueous silica sol in the presence of a catalyst. The aqueous system is virtually solvent-free and is suitable for metal coatings. Disadvantageous is the high cross-linking temperature of 200 ° C.

  U.S. Pat. No. 6,468,336 describes the formulation and use of anticorrosion coatings for steel. The water-based formulation contains water glass as binder and zinc, iron-containing layered silicate as well as further fillers as pigments. Said formulation is said to achieve excellent corrosion protection with a layer thickness of 15-25 μm.

  European Patent (EP) 1 191 075 teaches a water-based binary system for anticorrosion coating on steel. The first component contains water, aminoalkyltrialkoxysilane, acid, epoxy silane and a conductive pigment. The second component consists of zinc powder. The finished mixture is said to allow a processing time of 16 hours. The alcohol from the hydrolysis of the silane was not removed, and the aqueous system was applied to produce a dry film thickness of 25 μm. The coated sheet showed no corrosion after 7 months of outdoor exposure.

  International Publication (WO) No. 2000/46311 describes the treatment of metal substrates with a formulation comprising ureidosilane, polyfunctional silylsilane and solvent. The silane is first partially hydrolyzed and subsequently compounded. The hydrolyzed alcohol is not removed and the formulation is used without pigment.

  International Publication (WO) No. 2002/22745 claims the protection of the solventless anticorrosive primer patent. The primer is composed of stabilized silica sol, layered silicate, calcined aluminum-containing layered silicate and zinc dust. The dry film thickness of the coating is about 15-25 μm. Its wear resistance and processing time were measured.

  International Publication (WO) 2003/022940 describes a corrosion protection system consisting of an aqueous silica sol, optionally an organic resin, zinc dust and further additives. The system is characterized by its wear resistance and pencil hardness.

  WO 2006/079516 relates to aqueous binders or coatings based on aminoalkyl silanes or formylaminopropyltrialkoxysilanes and epoxy silanes.

  In EP-B1 1 191 075, the binder is based on aminoalkylalkoxysilanes and epoxy-functional alkoxysilanes and well-defined production methods. The coating agent disclosed therein was formulated based on the binder with the addition of pigments, especially conductive pigments and additives.

  International Publication (WO) No. 99/14277 discloses an aqueous primer composition comprising a reactive resin (dispersion), an organofunctional silane (aminosilane or epoxysilane, not bissilylsilane), and a curing reagent. Things are listed. The adhesion of the metal substrate treated with this primer, in combination with an epoxy resin, shows very good strength in a shear test.

  International Publication (WO) 2008/133916 describes a method for treating metal surfaces. The method involves treatment with an aqueous formulation consisting of hydrolyzed / condensed silane. The silane used may be an aminosilane having a hydroxyl group. The coating system thus produced is not solventless. The treated metal substrate is painted and shows less creepage from the stamp as compared to the standard treatment.

  US Pat. No. 6,929,826 claims protection of a patent for a method of surface treating a metal. The method includes treatment with a formulation containing epoxy silane and tetraalkoxy silane.

  International Publication (WO) No. 2006/137663 describes a composition comprising aminosilane and epoxysilane. Furthermore, the formulation contains magnesium and vanadium compounds and an acid. The production takes place in a water / alcohol mixture. Metal substrates treated with this formulation exhibit good corrosion resistance and good adhesion to organic coatings. The system is not solventless.

  International Publication (WO) 2009/059798 discloses metal formulations and coatings. The formulation consists of tetraethoxysilane, vinyltrimethoxysilane, phenyltriethoxysilane, and propyltrimethoxysilane. Furthermore, patent protection of further components such as alcohols, catalysts, silica sols and additives is claimed. The coating according to the invention must be heated for curing. The formulation is said to protect the metal substrate from corrosion.

  EP 0 274 428 teaches a composition consisting of alkyltrialkoxysilanes, vinyltrialkoxysilanes and / or further silanes such as epoxy silanes, organic solvents and aluminum sols.

  International Publication (WO) 2009/030538 teaches an aqueous composition based on bisalkoxyalkylsilylamines which is essentially free of organic solvents and does not release alcohol upon crosslinking. . Furthermore, such systems may be based on further organosilanes such as 3-glycidyloxypropyltrialkoxysilane as well as alkylalkoxysilanes. The system may also contain fillers such as silicic acid, titanium dioxide and aluminum oxide, and colored pigments. Furthermore, the production method and the use—especially as an anticorrosion coating—are disclosed.

  Silane and aqueous silane systems can form coatings on many substrates in the case of corresponding formulations. These coatings are not active anticorrosion, can only form a passive corrosion layer, and can act as a binder or crosslinker in the coating compositions. And a binder can also be regarded as a crosslinking agent. Active corrosion protection can be achieved with a corrosion inhibitor. In order to be able to produce such a formulation, in particular an environmentally friendly aqueous formulation, the binder and the anticorrosive additive provide a stable and effective formulation as much as possible, and are suitable on an industrial scale. Must be compatible so that it can be processed within.

European Patent (EP) No. 0590270 German Patent Application Publication (DE) No. 10335178 U.S. Patent No. 5,051,129 European Patent (EP) No. 0716128 International Publication (WO) No. 2000/39177 U.S. Patent No. 6,955,728 International Publication (WO) No. 2004/076717 International Publication (WO) No. 2004/076718 U.S. Patent No. 5,206,285 European Patent Application Publication (EP) No. 1760128 German Patent Application Publication (DE) No. 102004037045 U.S. Patent No. 6,468,336 European Patent (EP) No. 1191075 International Publication (WO) No. 2000/46311 International Publication (WO) No. 2002/22745 International Publication (WO) No. 2003/022940 International Publication (WO) No. 2006/079516 European Patent (EP-B1) No. 1191075 International Publication (WO) No. 99/14277 International Publication (WO) No. 2008/133916 U.S. Patent No. 6,929,826 International Publication (WO) No. 2006/137663 International Publication (WO) No. 2009/059798 European Patent (EP) 0274428 Specification International Publication (WO) No. 2009/030538

  Therefore, the present invention is based on the problem of providing a further VOC-free further aqueous anticorrosive composition based on so-called bisaminosilane cocondensates as binders, in which these binders are Is essentially compatible with the particulate additive as well as optionally further additives, and is itself shelf-stable for at least several hours to several weeks until application. Furthermore, a particular concern was that such formulations can be cured at room temperature and achieve good adhesion and corrosion protection on metal substrates. Furthermore, the anticorrosion coatings obtainable on this basis can be applied in various film thicknesses and have a good ueberlackierbar after the curing, ie coatings, in particular organic (paint) coatings Efforts have been made to achieve good adhesion to.

  According to the invention, the problem has been solved in accordance with the features in the claims.

  And an epoxy alkyl functional alkoxysilane, see formula I below, a virtually fully hydrolyzed cocondensate, and at least one bisaminoalkyl functional alkoxysilane, see also formulas II and IIa below. , And optionally as a base with further organofunctional alkoxysilanes or silica sol systems, special aqueous binders for anticorrosive formulations having defined pH values and defined dry residues can be prepared, said binders Is substantially free of VOC, hardens at low temperatures in air, ie preferably at room temperature, preferably at 16-26 ° C., in particular at 20 ° C., and is a particulate metal, metal alloy and / or metal compound, In particular, it is preferably compatible and storage-stable with additives from among metal oxides or metal salts and optionally further additives. And it can be applied has been found surprisingly. Furthermore, the composition can be used to advantageously produce a thin film on the metal, on which a further coating is applied and at the same time good adhesion to the primer or the metal is achieved. Can do.

  Binders are typically liquids that attach solids with a fine degree of dispersion and that can further crosslink in the formulation and allow adhesion to the substrate. In order for a blend of binder and particulate additive to be produced, the binder must be compatible with the additive, i.e., wet the additive. Thereby, the additive can be dispersed in the binder and the advantageous properties of the system can be obtained. Blends of binders and additives can be widely used, for example, in corrosion protection. Particularly advantageous here are aqueous systems, since they are essentially free of organic solvents or other substances harmful to the environment. Aqueous sol-gel systems are not only environmentally friendly, they can be very varied and can be used in a wide variety of ways. The novel binders based on aqueous sol-gel systems can not only cure at low temperatures, they also improve the adhesion of further coatings on these systems, i.e. they have good topcoat compatibility. is there.

  The range of use of the aqueous binder is extremely diverse. They can be used as main agents for various formulations, in particular as binders, in combination with particulate metals and / or particulate metal compounds and optionally further additives. If the system is hydrophobic, in addition to the epoxy-functional alkoxysilane and the bisamino-functional alkoxysilane, alkyltrialkoxysilanes can also be used as a further component. In cases where special properties of the aqueous binder system or special functions for bonding to the organic coating system are required, further organofunctional silanes or tetraalkoxysilanes can also be added to the epoxy functional alkoxysilane and the bisamino functional group. In addition to the functional alkoxysilane, it can be used. The ratio of the silane component is preferably such that the fully hydrolyzed and condensed product is stable in the aqueous solution and nevertheless at low temperatures on the substrate or in the formulation Can be adjusted to cure. However, not only the ratio but also the order of metering has an essential influence on the product properties. The hydrolyzed alcohol is advantageously removed from the reaction system during the production of the binder, so that a substantially VOC-free aqueous product can be supplied.

  Also, the lower the proportion of the epoxy functional alkoxysilane in the binder, and the higher the proportion of the bisamino functional alkoxysilane, see also Formula II, the higher the silane weight in the aqueous formulation. It has also been found that more and more minutes can be selected. The binder agent is typically composed of a fully hydrolyzed and at least partially condensed or cocondensed silane. In order to obtain a storage stable silane system, the solids content of the pure epoxy functional alkoxysilane in the aqueous sol-gel system can advantageously be up to 70% by weight, whereas the solids content of the pure bisamino functional alkoxysilane is Should be no more than about 10% by weight to avoid solids. The condensate or cocondensate dry residue (also referred to herein as solids) in the binder is preferably 1-50% by weight, particularly preferably 3-45% by weight and very particularly preferably 5-35% by weight. %.

The subject of the present invention is therefore
Formula I
_{^{X-Si (R 2) x}} (OR 1) 3-x (I)
[Wherein, X represents a 2- (3,4-epoxycyclohexyl) ethyl group, a 1-glycidyloxymethyl group, a 2-glycidyloxyethyl group, a 3-glycidyloxypropyl group or a 3-glycidyloxyisobutyl group, R ^{1 and} R ² are each independently a linear or branched alkyl group having 1 to 4 carbon atoms, and x is equal to 0 or 1.]-Glycidyloxyalkylalkoxy Silane,
Formula II
(OR ¹ ) ₃ Si-A-Si (OR ¹ ) ₃ (II)
In which the radicals R ¹ are the same or different and R ¹ is a linear or branched alkyl group having 1 to 4 carbon atoms, and A is of the formula IIa
_{- (CH 2) i - [} NH (CH 2) f] g NH [(CH 2) f * NH] g * - (CH 2) i * - (IIa)
Represents a bisamino functional group represented by
Here, i, i *, f, f *, g or g * are the same or different, i and / or i * = 1, 2, 3 or 4, f and / or f * = 1 or 2, g And / or g * = 0 or 1, preferably i and i * are equal to 3, and g and g * are equal to 0, and R ¹ represents methyl and / or ethyl. A species of bis (alkoxysilylalkyl) amine, and
Optionally, at least one further from among tetraalkoxysilane, alkylalkoxysilane, mercaptoalkylalkoxysilane, aminoalkylalkoxysilane, carboxyalkylalkoxysilane, ureidoalkylalkoxysilane, thiocyanatoalkylalkoxysilane and silica sol. A binder containing at least one cocondensate based on a silicon compound;
·water,
An alcohol in an amount of less than 3% by weight, preferably 0.01-2.5% by weight, in particular 0.1-2.2% by weight, based on the composition;
A composition comprising at least one additive and optionally at least one additive from among particulate metals, metal alloys and / or metal compounds;
In doing so, the pH value in the composition is 1-14, preferably 2-13, in particular including all positive numbers ≧ 2.5- ≦ 12, 3.0; 3.5; 0; 4.5; 5.0; 5.5; 6.0; 6.5; 7.0; 7.5; 8.0, and the dry residue of the binder determines the binder used. As a reference, 1 to 50% by weight, preferably 5 to 40% by weight, particularly preferably 8 to 35% by weight, in particular 10 to 25% by weight, and 2, 3, 4, 6, 7, 9, 11, 12 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24 mass%.

The binder for the composition according to the invention can advantageously be prepared as follows, first of all in molar excess based on the silanes used according to formulas I and II and optionally on said silicon compounds: Charge water, adjust to an acidic pH value with the addition of organic or inorganic acids, and optionally add silica sol at that time,
Metering and heating an ω-glycidyloxyalkylalkoxysilane of formula I;
Optionally, after metering acid,
And at least one bis (alkoxysilylalkyl) amine of the general formula II and optionally tetraalkoxysilane, alkylalkoxysilane, aminoalkylalkoxysilane, ureidoalkylalkoxysilane, carboxyalkylalkoxysilane and thiocyanatoalkylalkoxysilane. Metering at least one further silicon compound from within,
And react,
Subsequently, the hydrolyzed alcohol produced in the process is at least partially removed from the reaction mixture under reduced pressure (anteilig),
The binder thus obtained is optionally diluted with water and / or an aqueous acid solution (waessrigen Saeure) and subsequently filtered,
In that case, the dry residue of the binder is 1 to 50% by weight, preferably 5 to 40% by weight, particularly preferably 8 to 35% by weight, in particular 10 to 25% by weight, based on the binder used. It is.

  The composition according to the invention is preferably present as a one-component system and can be used.

  However, it can also be used by taking the binder and at least one of the additives as a two-component system, mixing the components before the application, thus obtaining the corresponding composition. In doing so, further additives may also be added.

  Advantageously, the composition according to the invention has a dry residue (solid content) of from 1 to 50% by weight, preferably from 3 to 45% by weight, particularly preferably from 3 to 35% by weight, based on the composition.

  Furthermore, the composition according to the invention comprises 1 to 95% by weight, preferably 3 to 90% by weight, particularly preferably 5 to 85% by weight and very particularly preferably 10 to 80% by weight of the particulate metal in the composition. And / or by the content of metal compounds.

  Thus, as additives in the composition, preferably granular metals, metal alloys and / or metal compounds, in particular conductive or non-conductive fillers, zinc powder, zinc lamellae, zinc dust, made of zinc alloys, For example, zinc bismuth alloy, magnesium and magnesium alloy powder or lamella, aluminum powder, aluminum lamella, aluminum alloy powder and lamella, titanium dioxide, red iron oxide, yellow iron oxide, calcium carbonate, talc, aluminum silicate , Barium sulfate, kaolin, magnesium silicate, crystalline quartz, amorphous quartz, magnesium magnesium carbonate, calcium silicate, aluminum oxide, zeolite, wollastonite, zinc oxide, zinc phosphate, bismuth vanadate, lead chromate , Silicon carbide and inorganic colored pigments Is-option, a metal oxide.

  In that case, the particulate additive advantageously has a particle size of 5 nm to 50 μm, preferably 10 nm to 40 μm, particularly preferably 15 nm to 30 μm. The particle size can be measured using, for example, Retsch Technology's CAMSIZER, HORIBA LA-30, LB-550 and LA-950. For example, the particle size can be measured from 1 nm wet and from 100 nm dry.

  In particular, the conductive additive protects against corrosion when used in sufficient concentration and in contact with the metal substrate. Metal bodies that are protected against corrosion by a coating made of granular metal can then be advantageously welded.

  Furthermore, the compositions according to the invention additionally comprise antifoaming agents, thickeners, rheology aids (Rheologiehilfsmittel), dispersion aids, antisettling agents, rust inhibitors, wetting agents, organic pigments, polymers or polymer dispersions. Additives advantageously selected from the liquid and the condensation and curing catalyst may be included. And as a polymer, for example but not limited to: acrylate dispersion, PU dispersion, epoxy resin dispersion, functionalized polyester, water-soluble polymer such as PVA, polyacrylic acid-some suitable polymers You may use-just to name. In addition, organic film-forming elements and adhesion promoters based on acrylic esters, acrylic-polyester-polyurethane copolymers, ethylene-acrylic copolymers, polyester resins with free carboxyl groups are used as additives or polymers or co-binders. You can do it.

  And the compositions according to the present invention are each based on 0 to 5% by weight of additives, in particular 0 to 5% by weight of thickener and / or 0 to 5% by weight of anti-settling agent, based on the composition. May be characterized by a content of 0 to 3% by weight of wetting agent and / or 0 to 1% by weight of corrosion inhibitor, wherein the total of all components present in the composition is 100% by weight %.

  Typical thickeners are, for example, polyacrylic acid polymers, cellulose ethers, polyurethanes, acrylate polymers, hydroxyethyl cellulose, which are 0.005 to 4.0% by weight, preferably 0.008 to 3.0% by weight. % And very particularly preferably in a concentration of 0.01 to 2.0% by weight. Examples of thickeners or rheology modifiers are, inter alia, Coapur Coapur 6050 and Coapur XS 71 from Coatex.

  Examples of anti-settling agents are, inter alia, Laponite, bentonite, glyceryl stearate, polyamide, xanthan, polyethylene wax, modified and unmodified pyrogenic silica, such as Aerosil® R 812 S or Aerosil® R 805, which are likewise used in concentrations of up to 4% by weight, preferably 0.01-3% by weight, in particular 0.1-2% by weight.

  Typical wetting agents may include, for example, BYK 348 as well as ethoxylated alcohols, which are up to 3% by weight, preferably 0.01 to 2.5% by weight or very particularly preferably 0.1 to 1.5%. Used at a concentration of mass%.

  Typical corrosion inhibitors are molybdates, phosphates, chromates, borates and in particular organic corrosion inhibitors. The organic corrosion inhibitor is preferably in a slightly lower concentration, each based on the composition, preferably up to 1.0% by weight, preferably up to 0.8% by weight, particularly preferably 0.5% by weight. Up to, in particular, 0.00001 to 0.1% by weight, in which case the total of all components present in the composition is 100% by weight.

  Possible catalysts for the condensation and curing are, for example, TYZOR LA (DuPont), titanium acetylacetonate, tetrakis (triethanolamine) zirconate.

Furthermore, the subject of the present invention is a process for the production of a composition according to the invention,
First of all, the formula I
_{^{X-Si (R 2) x}} (OR 1) 3-x (I)
[Wherein, X represents a 2- (3,4-epoxycyclohexyl) ethyl group, a 1-glycidyloxymethyl group, a 2-glycidyloxyethyl group, a 3-glycidyloxypropyl group or a 3-glycidyloxyisobutyl group, R ^{1 and} R ² are each independently a linear or branched alkyl group having 1 to 4 carbon atoms, and x is equal to 0 or 1.] Alkoxysilane,
Formula II
(OR ¹ ) ₃ Si-A-Si (OR ¹ ) ₃ (II)
In which the radicals R ¹ are the same or different and R ¹ is a linear or branched alkyl group having 1 to 4 carbon atoms, and A is of the formula IIa
_{- (CH 2) i - [} NH (CH 2) f] g NH [(CH 2) f * NH] g * - (CH 2) i * - (IIa)
Represents a bisamino functional group represented by
Here, i, i *, f, f *, g or g * are the same or different, i and / or i * = 1, 2, 3 or 4, f and / or f * = 1 or 2, g And / or g * = 0 or 1, preferably i and i * are equal to 3, and g and g * are equal to 0, and R ¹ represents methyl and / or ethyl. One bis (alkoxysilylalkyl) amine and
And optionally at least one further from among tetraalkoxysilane, alkylalkoxysilane, mercaptoalkylalkoxysilane, carboxyalkylalkoxysilane, aminoalkylalkoxysilane, ureidoalkylalkoxysilane, thiocyanatoalkylalkoxysilane and silica sol. A binder containing at least one cocondensate based on a silicon compound is prepared as follows: molar excess based on the silane used according to formulas I, II and optionally on said silicon compound An amount of water is charged, adjusted to an acidic pH value with the addition of organic or inorganic acids, and optionally silica sol is added with stirring,
Metering and heating an ω-glycidyloxyalkylalkoxysilane of formula I;
Optionally, after metering acid,
And at least one bis (alkoxysilylalkyl) amine of general formula II and optionally tetraalkoxysilane, alkylalkoxysilane, mercaptoalkylalkoxysilane, aminoalkylalkoxysilane, carboxyalkylalkoxysilane, ureidoalkylalkoxysilane and Metering and reacting with at least one further silicon compound from among the cyanatoalkylalkoxysilanes;
Subsequently, the hydrolyzed alcohol produced thereby is at least partially removed from the reaction mixture under reduced pressure,
The binder thus obtained is optionally diluted with water and / or an aqueous acid solution and subsequently filtered,
And by dispersing at least one additive from the particulate metal, metal alloy and / or metal compound in the binder thus obtained, and optionally stirring at least one additive. It is characterized.

  In so doing, the binder formulation is preferably 0.1 to 99.9 to 99 to 1, preferably 1 to 99 to 95 to 5, particularly preferably ω-glycidyloxyalkylalkoxysilane of formula I. Is used in a molar ratio (formula I to II) to bis (alkoxysilylalkyl) amines of the general formula II of ˜80: 20, very particularly preferably of ˜70: 30, in particular the ω-glycidyloxyalkylalkoxysilane In the binder, 0.001 to 42 mol%, preferably 0.01 to 30 mol%, particularly preferably 0.1 to 15 mol%, very particularly preferably 0.2 to 1.5 mol% is used.

  In particular, in the case of the process according to the invention, a molar excess of water is bound to the Si in which the silane used is present, based on the silane used according to formulas I and II and optionally on said silicon compounds. Suitably, 2 to 1000 moles of water, preferably 5 to 500 moles, in particular 10 to 100 moles of water per mole of alkoxy groups are charged under protective gas. In the reaction, nitrogen or argon is usually used as a protective gas.

  Furthermore, in carrying out the process according to the invention, organic or inorganic acids may be used, which acids are preferably selected from among formic acid, acetic acid, propionic acid, hydrochloric acid, nitric acid, sulfuric acid, phosphoric acid. Is selected. The acid can be used in an aqueous type, but also in a concentrated type. In particular, using one of the acids mentioned above, preferably formic acid, the pH value of the reaction mixture or product mixture, in particular the binder, is 1 to 6.5, during and / or after the reaction, It can preferably be adjusted to 2-6, in particular 2.5; 3; 3.5; 4; 4.5; 5 and 5.5.

  Surprisingly, it has been found that some of the binders used according to the invention can be stabilized in the neutral as well as in the alkaline region. And, for example, by adding an aqueous alkaline solution or a suitable base, the pH value is advantageously neutral as well as alkaline, in particular 7; 7.5, 8; 8.5; 9; 9.5; 10; 10.5 11; 11.5; 12; 12.5; 13 and 14, see Examples. Further bases other than alkaline solutions such as aqueous NaOH or KOH that can be used advantageously are also preferably N, N-dimethylethanolamine or TYZOR TEAZ [tetrakis (triethanolamine) zirconate].

  Furthermore, in the process according to the invention, preferably 3-glycidyloxypropyltrimethoxysilane and / or 3-glycidyloxypropyltriethoxysilane is used as the ω-glycidyloxyalkylalkoxysilane of the formula I, The resulting acidic aqueous mixture is metered and the mixture is stirred at 50-90 ° C., preferably with stirring or mixing for 0.1-3 hours, preferably 0.5-1.5 or 2 hours. Is heated to a temperature of 55-70 ° C, in particular 60-65 ° C.

Subsequently, the bis (trimethoxysilylpropyl) amine and / or bis (triethoxysilylpropyl) amine is preferably metered into the heated acidic mixture containing ω-glycidyloxyalkylalkoxysilane. In addition, for example together with the bis (alkoxysilylalkyl) amine, optionally as further silicon compounds, tetraalkoxysilanes, preferably tetramethoxysilane, tetraethoxysilane, alkylalkoxysilanes, preferably C ₁ -C _16- alkylalkoxysilanes, especially methyltrimethoxysilane, methyltriethoxysilane, n-propyltrimethoxysilane (PTMO), n-propyltriethoxysilane (PTEO), isobutyltrimethoxysilane (IBTMO), isobutyltriethoxysilane ( IBTEO), octyltrimethoxysilane (OCCTMO), octyltriethoxysilane (OCTEO), mercaptoalkylalkoxysilane, preferably 3-mercaptopropyltrimethoxysilane (MTMO) , Mercaptopropyltrimethoxysilane (MTEO), aminoalkylalkoxysilane, preferably 3-aminopropyltrimethoxysilane (AMMO), 3-aminopropyltriethoxysilane (AMEO), N- (2-aminoethyl) -3- Aminopropyltrimethoxysilane (DAMO), N- (2-aminoethyl) -3-aminopropyltriethoxysilane, N, N'-diaminoethyl-3-aminopropyltrimethoxysilane (TriAMO), N, N'- Diaminoethyl-3-aminopropyltriethoxysilane, ureidoalkylalkoxysilane, preferably 3-ureidopropyltrimethoxysilane, 3-ureidopropyltriethoxysilane, and / or thiocyanatoalkylalkoxysilane, preferably 3-thio Cyanatopropyltrimethoxysilane, 3-thiocyanatopropyltrimethoxysilane, carboxyalkyltrialkoxysilane, preferably 4- (trimethoxysilyl) butanoic acid, 5- (trimethoxysilyl) pentanoic acid, 5- (triethoxy Silyl) pentanoic acid may be used. In doing so, the metering of the silane is advantageously carried out at a pH value of 2-6, preferably 3-5, and at 50-90 ° C., preferably 60-65 ° C. with stirring. Subsequently, the mixture can advantageously be reacted for a further 0.3 to 6 hours, preferably 2 to 4 hours, during which time it can be further stirred; that is, the alkoxysilane used is hydrolyzed during that time. Essentially complete hydrolysis and condensation or co-condensation.

  From the product mixture thus obtained, the hydrolyzed alcohol which is subsequently produced during the reaction and which usually has a water content can be at least partly removed from the reaction mixture under reduced pressure (vacuum distillation).

  The binder thus present may optionally be diluted with water and / or an aqueous acid or base solution, for example to adjust the pH value, the dry residue content and / or the viscosity. Subsequently, the binder is preferably filtered, in which case preferably a microporous filter sheet is used to separate the coarser agglomerates optionally formed during the reaction. The binders thus obtained have a generally oily consistency at room temperature, are slightly turbid or clear, and are yellowish or colorless.

  In the binder thus obtained, at least one additive from the particulate metals, metal alloys and / or metal compounds already disclosed above is now dispersed and optionally also indicated above. At least one additive can be incorporated.

  Furthermore, according to the invention, an organic or inorganic acid selected from formic acid, acetic acid, propionic acid, hydrochloric acid, nitric acid, sulfuric acid, phosphoric acid and caustic soda, caustic potash or "TYZOR TEAZ" [tetrakis (triethanolamine) -Zirconate] or N, N-dimethylethanolamine or an aqueous base solution selected from other bases is preferably used, wherein the pH value is determined during the reaction in the binder and / or the reaction. After and / or after compounding in the composition, 1 to 14, preferably 2 to 12, particularly preferably 2.5 to 9, very particularly preferably 3 to 8, in particular 3.5; 4; 4 .5; 5; 5.5; 6; 6.5; 7; 7.5; 8 and 8.5, in which case said particulate metal, metal alloy and / or metal already to the binder At least one of the compounds Pressure, especially zinc to regulated binder acidic, zinc oxide, zinc alloy, magnesium, aluminum, magnesium alloy, aluminum alloy or micaceous iron oxide, is also added, for example MIOX Micron, can result in change of the pH value.

  The composition according to the invention can be produced in a mixer or mixing apparatus which is corresponding and known per se to the person skilled in the art.

  Furthermore, the subject of the invention is according to or in accordance with the invention for coatings which cure in air at temperatures of from 16 to 26 ° C., particularly advantageously for coating metals and metal alloys to protect against corrosion. Use of the composition that can be obtained.

  For example, these special compositions according to the invention are particularly advantageously superior in comparison to excellent processing stability and user-friendly and environmentally friendly properties for corrosion protection applications on metal substrates.

  The invention is explained in more detail by the following examples, which do not limit the subject of the invention.

Example:
Chemicals and abbreviations used:

Additive:

Analysis survey:
Measurement of pH value:
The pH value of the reaction mixture was measured using pH test paper (specific area indicator pH 2.5-4.5, Merck; pH-Fix 0.0-6.0, Macherey-Nagel)
Measurement of the pH value in the binder and the composition formulated therefrom was optionally performed using a Metrohm 826 pH mobile pH meter. The formulation was diluted 1: 1 with water before the measurement.

Measurement of the dry residue (solid content):
The aqueous silane based solids (also referred to as dry residue) were measured as follows:
1 g of sample was weighed into a small porcelain dish and dried to constant weight at 105 ° C. in a dryer.

Measurement of the SiO ₂ content:
Samples 1.0-5.0 g were mixed with 1 Kjeldahl tablet and 20 ml sulfuric acid in a 400 ml beaker and first slowly heated. At that time, the beaker was covered with a watch glass. The sulfuric acid smoked vigorously, all organic components were decomposed, and the temperature was increased until the solution became clear and pale. The cold degradation solution was diluted to about 200 ml with distilled water and boiled briefly (running the water at the edge of the beaker under the acid). The residue was filtered through white ribbon filter paper and washed with hot water until the wash water exhibited a pH value of> 4 (pH test paper). The filter paper was dried in a platinum crucible, incinerated, and ignited in a muffle furnace at 800 ° C. for 1 hour. The residue was abgeraucht after weighing and the crucible was ignited using a blast burner, optionally once again at 800 ° C. and weighed after the cooling. The difference between the two weighings corresponded to the SiO ₂ content.
Evaluation: D × 100 / E = SiO ₂ mass%
D = mass difference before and after defluorination (Abfluorieren) [mg]
100 = converted to% E = measured amount [mg].

Measurement of the free methanol content and ethanol content:
The alcohol measurement was performed using GC.
Column: RTX 200 (60m)
Temperature program: 90-10-25-240-0
Detector: FID
Injection volume: 1.0 μl
Internal standard: 2-butanol.

Example 1
In a 2 l stirrer equipped with a metering device and a reflux condenser, 1328.26 g of water and 1 g of formic acid (HCOOH = 85% by mass) were charged under a nitrogen atmosphere. 90.0 g of 3-glycidyloxypropyltrimethoxysilane (GLYMO) was metered in (pH measured after the addition = 3.4), heated to 65 ° C. and stirred for 1 hour. 27.0 g of formic acid (HCOOH = 85% by weight) was added and 210.0 g of Dynasylan® 1122 was metered in via the metering device. The mixture was stirred after 3 hours at 65 ° C. with a pH value of 4.94. Finally, at about 130 mbar, 362.93 g of alcohol / water mixture were removed by distillation. 400.0 g of water was added to the gel batch. The residue cooled to room temperature was filtered through a Seitz T-950 filter sheet. The final mass of the residue was 1681.4 g.
A yellowish clear liquid having a pH value of 5.6 was obtained. The product is shelf stable for at least 6 months.
Dry residue: 11.82% by weight
SiO ₂ content: not measured Free methanol: 0.6% by mass
Free ethanol: 1.5% by mass.

Example 2
A 2 l stirrer equipped with a metering device and a reflux condenser was charged with 1336.0 g of water and 2 g of formic acid (HCOOH = 85% by mass) under a nitrogen atmosphere. 150.0 g of GLYMO was metered in (pH after the addition = 3.0), heated to 65 ° C. and stirred for 1 hour. 19.0 g of formic acid (HCOOH = 85% by weight) was added and 150.0 g of Dynasylan® 1122 was metered in via the metering device. 2.94 g of formic acid (HCOOH = 85% by weight) was post-weighed. After stirring for 3 hours at 65 ° C. at a pH value of 3.82, 1.29 g of formic acid (HCOOH = 85% by weight) were again metered in. Finally, at a pH of 3.8 and about 170 mbar, 318.07 g of alcohol / water mixture was removed by distillation. To the batch was added 27.67 g of water. The residue cooled to room temperature was filtered through a Seitz T-950 filter sheet. The final mass of the residue was 1312.33 g.
A yellowish clear liquid having a pH value of 4.3 was obtained. The product is shelf stable for at least 6 months.
Dry residue: 14.9% by mass
SiO ₂ content: 5.9% by mass
Free methanol: 1.1% by mass
Free ethanol: 1.1% by mass.

Example 3
In a 2 l stirrer equipped with a metering device and a reflux condenser, 1338.3 g of water and 2 g of formic acid (HCOOH = 85% by mass) were charged under a nitrogen atmosphere. 180.0 g of GLYMO was metered in (pH after the addition = 2.5), heated to 65 ° C. and stirred for 1 hour. 16.7 g of formic acid (HCOOH = 85% by mass) was added and 120.0 g of bis AMEO was metered in via the metering device. 1.5 g of formic acid (HCOOH = 85% by weight) was metered in afterwards. The mixture was stirred after 3 hours at 65 ° C. at a pH value of 3.8 to 4.0. Finally, at about 200 mbar, 342.12 g of alcohol / water mixture was removed by distillation. To the batch was added 74.79 g of water. The residue cooled to room temperature was filtered through a Seitz T-950 filter sheet. The final mass of the residue was 1280.21 g.
A yellowish clear liquid having a pH value of 5.0 was obtained. The product is shelf stable for at least 6 months.
Dry residue: 15.7% by weight
SiO ₂ content: 5.7% by mass
Free methanol: 0.7% by mass
Free ethanol: 0.5% by mass.

Example 4
In a 2 l stirrer equipped with a metering device and a reflux condenser, 1329.2 g of water and 2 g of formic acid (HCOOH = 85% by mass) were charged under a nitrogen atmosphere. 120.0 g of GLYMO was metered in (pH after the addition = 2.5), heated to 65 ° C. and stirred for 1 hour. 25.9 g of formic acid (HCOOH = 85% by weight) was added and 180.0 g of bis AMEO was metered in via the metering device. The mixture was stirred at 65 ° C. for 3 hours at a pH value of 4.0. Finally, at about 200 mbar, 344.57 g of alcohol / water mixture was removed by distillation. To the batch was added 20.18 g of water. The residue cooled to room temperature was filtered through a Seitz T-950 filter sheet. The final mass of the residue was 1304.02 g.
A yellowish clear liquid having a pH value of 4.4 was obtained. The product is shelf stable for at least 6 months.
Dry residue: 15.0% by mass
SiO ₂ content: 6.1% by mass
Free methanol: 0.7% by mass
Free ethanol: 1.1% by mass.

Example 5
In a 2 l stirrer equipped with a metering device and a reflux condenser, 1319.6 g of water and 2 g of formic acid (HCOOH = 85% by mass) were charged under a nitrogen atmosphere. 60.0 g of GLYMO was metered in (pH after the addition = 2.5), heated to 65 ° C. and stirred for 1 hour. 34.5 g of formic acid (HCOOH = 85% by mass) was added and 240.0 g of bis AMEO was metered in via the metering device. The mixture was stirred after 3 hours at 65 ° C. at a pH value of 3.8 to 4.0. Finally, at about 200 mbar, 356.64 g of alcohol / water mixture were removed by distillation. To the batch, 95.71 g of water was added to reach 15% theoretical solids. However, because the viscosity was too high, it was additionally diluted to about 10% solids with 272.2 g of water. The residue cooled to room temperature was filtered through a Seitz T-950 filter sheet. The final mass of the residue was 1472.29 g.
A yellowish clear liquid having a pH value of 4.4 was obtained.
The product is shelf stable for at least 6 months.
Dry residue: 10.4% by mass
SiO ₂ content: 4.3% by mass
Free methanol: 0.2% by mass
Free ethanol: 0.6% by mass.

Example 6
Under a nitrogen atmosphere, 1346.3 g of water and 2 g of formic acid (HCOOH = 85% by mass) were charged in a 2 l stirrer equipped with a metering device and a reflux condenser. 210.0 g of GLYMO was metered in (pH after the addition = 2.5), heated to 65 ° C. and stirred for 1 hour. 11.73 g of formic acid (HCOOH = 85% by mass) was added, and 90.0 g of bis AMEO was metered in via the metering device. The mixture was stirred at 65 ° C. for 3 hours at a pH value of 4.0. Finally, at about 180 mbar, 335.16 g of alcohol / water mixture were removed by distillation. To the batch was added 72.14 g of water. The residue cooled to room temperature was filtered through a Seitz T-950 filter sheet. The final mass of the residue was 1299.86 g.
A yellowish clear liquid having a pH value of 4.2 was obtained.
The product is shelf stable for at least 6 months.
Dry residue: 15.6% by mass
SiO ₂ content: 5.8% by mass
Free methanol: 1.1% by mass
Free ethanol: 0.5% by mass.

Example 7
In a 2 l stirrer equipped with a metering device and a reflux condenser, 1347.9 g of water and 2 g of formic acid (HCOOH = 85% by mass) were charged under a nitrogen atmosphere. 240.0 g of GLYMO was metered in (pH after the addition = 2.5), heated to 65 ° C. and stirred for 1 hour. 7.1 g of formic acid (HCOOH = 85% by mass) was added and 60 g of bis AMEO was metered in via the metering device. The mixture was stirred at 65 ° C. for 3 hours at a pH value of 4.0 to 4.5. In the meantime, 3.0 g of formic acid (HCOOH = 85% by weight) was post-weighed to reach pH 3.5. Finally, at about 180 mbar, 295.81 g of alcohol / water mixture was removed by distillation. To the batch was added 50.62 g of water. The residue cooled to room temperature was filtered through a Seitz T-950 filter sheet. The final mass of the residue was 1333.38 g.
A yellowish clear liquid having a pH value of 5.2 was obtained.
The product is shelf stable for at least 6 months.
Dry residue: 16.2% by weight
SiO ₂ content: 5.6% by mass
Free methanol: 1.4% by mass
Free ethanol: 0.4% by mass.

Example 8
In a 2 l stirrer equipped with a metering device and a reflux condenser, 1353.2 g of water and 2 g of formic acid (HCOOH = 85% by mass) were charged under a nitrogen atmosphere. 270 g of GLYMO was metered in (pH after the addition = 2.5), heated to 65 ° C. and stirred for 1 hour. 2.6 g of formic acid (HCOOH = 85% by weight) was added and 30.0 g of Dynasylan® 1122 was metered through the metering device. The mixture was stirred after 3 hours at 65 ° C. at a pH of 4.3. In the meantime, 1.1 g of formic acid (HCOOH = 85% by weight) was post-weighed to reach pH 4.0. Finally, at about 180 mbar, 289.82 g of alcohol / water mixture was removed by distillation. To the batch was added 43.64 g of water and 0.5 g of formic acid (HCOOH = 85% by weight) once more. The residue cooled to room temperature was filtered through a Seitz T-950 filter sheet. The final mass of the residue was 1355.06 g.
A yellowish clear liquid having a pH value of 4.8 was obtained.
The product is shelf stable for at least 6 months.
Dry residue: 16.2% by weight
SiO ₂ content: 5.3% by mass
Free methanol: 1.7% by mass
Free ethanol: 0.2% by mass.

Example 9
In a 2 l stirrer equipped with a metering device and a reflux condenser, 1524.8 g of water and 2 g of formic acid (HCOOH = 85% by mass) were charged under a nitrogen atmosphere. 180.0 g of GLYMO was metered in (pH after the addition = 2.0), heated to 65 ° C. and stirred for 1 hour. 15.0 g of formic acid (HCOOH = 85% by weight) was added and 105.0 g of Dynasylan® 1122 was metered in via the metering device. At a pH value of 4.0, 15.0 g of n-propyltrimethoxysilane (PTMO) was added and then stirred at 65 ° C. for 3 hours. Finally, at about 130 mbar, 585.35 g of alcohol / water mixture were removed by distillation. To the batch, 4.83 g of water and 0.90 g of formic acid (HCOOH = 85% by weight) once more were added. The residue cooled to room temperature was filtered through a Seitz T-950 filter sheet. The final mass of the residue was 1235.30 g.
A yellowish clear liquid having a pH value of 4.5 was obtained.
The product is shelf stable for at least 6 months.
Dry residue: 16.8% by weight
SiO ₂ content: 6.3% by mass
Free methanol: 0.3% by mass
Free ethanol: 0.1% by mass.

Example 10
In a 2 l stirrer equipped with a metering device and a reflux condenser, 1220.0 g of water and 2 g of formic acid (HCOOH = 85% by mass) were charged under a nitrogen atmosphere. 165.10 g of GLYMO was metered in (pH after the addition = 2.5), heated to 65 ° C. and stirred for 1 hour. 15.0 g of formic acid (HCOOH = 85% by mass) was added, and 105.0 g of bis AMEO was metered in via the metering device. At a pH value of 4.0, 30.0 g of PTMO were added and then stirred for 3 hours at 65 ° C. Finally, at about 130 mbar, 323.13 g of alcohol / water mixture were removed by distillation. To the batch was added 158.76 g of water. The residue cooled to room temperature was filtered through a Seitz T-950 filter sheet. The final mass of the residue was 1196.54 g.
A yellowish clear liquid having a pH value of 4.5 was obtained.
The product is shelf stable for at least 6 months.
Dry residue: 15.2% by weight
SiO ₂ content: 6.0% by mass
Free methanol: 1.4% by mass
Free ethanol: 0.7% by mass.

Example 11
In a 2 l stirrer equipped with a metering device and a reflux condenser, 1193.8 g of water and 2 g of formic acid (HCOOH = 85% by mass) were charged under a nitrogen atmosphere. Levasil 100S / 45 152.6 g followed by 210 g of GLYMO (pH after the addition = 3.8) was heated to 65 ° C. and stirred for 1 hour. 11.75 g of formic acid (HCOOH = 85% by weight) was added and 90 g of Dynasylan® 1122 was metered through the metering device. A total of 4.93 g of formic acid (HCOOH = 85% by weight) had to be added to reach a total of pH 3.8. Thereafter, the mixture was further stirred at 65 ° C. for 3 hours. Finally, at about 180 mbar, 374.22 g of alcohol / water mixture was removed by distillation. To the batch, 92 g of water was added. The residue cooled to room temperature was filtered through paint filter paper. The final mass of the residue was 1277.92 g.
A bright orange liquid having a pH value of 4.0 and turbid like milk was obtained.
The product is shelf stable for at least 6 months.
Dry residue: 20.3% by mass
SiO ₂ content: 9.7% by mass
Free methanol: 0.8% by mass
Free ethanol: 0.4% by mass.

Example 12
In a 2 liter stirring device equipped with a metering device and a reflux condenser, 1041.7 g of water and 3.63 g of formic acid (HCOOH = 85% by mass) were charged under a nitrogen atmosphere. 305.0 g of Levasil® 100S / 45, followed by 210 g of GLYMO (pH after the addition = 3.5), heated to 65 ° C. and stirred for 1 hour. 11.79 g of formic acid (HCOOH = 85% by mass) was added, and 90 g of bis AMEO was metered in via the metering device. An additional 6.67 g of formic acid (HCOOH = 85% by weight) had to be added to reach a total of pH 3.8. Thereafter, the mixture was further stirred at 65 ° C. for 3 hours. Finally, at about 120 mbar, 300.71 g of alcohol / water mixture was removed by distillation. To the batch was added 55.38 g of water. The residue cooled to room temperature was filtered through paint filter paper. The final mass of the residue was 1316.62 g.
A milky liquid having a pH value of 3.9 was obtained.
The product is shelf stable for at least 6 months.
Dry residue: 25.4% by weight
SiO ₂ content: 13.9% by mass
Free methanol: 1.0% by mass
Free ethanol: 0.5% by mass.

Example 13
Under a nitrogen atmosphere, 954.9 g of water and 2.16 g of formic acid (HCOOH = 85% by mass) were charged in a 2 l stirrer equipped with a metering device and a reflux condenser. 392 g of HP 1535 followed by 210.8 g of GLYMO (pH after the addition = 3.0) were heated to 65 ° C. and stirred for 1 hour. 11.79 g of formic acid (HCOOH = 85% by mass) was added, and 90 g of bis AMEO was metered in via the metering device. A total of 2.58 g of formic acid (HCOOH = 85% by weight) had to be added to reach a total pH of 4.0. Thereafter, the mixture was further stirred at 65 ° C. for 3 hours. Finally, at about 160 mbar, 291.96 g of alcohol / water mixture were removed by distillation. To the batch was added 12.23 g of water and 1.04 g of formic acid (HCOOH = 85 wt%). The residue cooled to room temperature was filtered through paint filter paper. The final mass of the residue was 1359.80 g.
A light yellow milky liquid with a pH value of 4.2 was obtained.
The product is shelf stable for at least 6 months.
Dry residue: 25.8% by weight
SiO ₂ content: 15.6% by mass
Free methanol: 1.5% by mass
Free ethanol: 0.7% by mass.

Example 14
In a 2 l stirrer equipped with a metering device and a reflux condenser, 501.8 g of water and 1.5 g of formic acid (HCOOH = 85% by mass) were charged under a nitrogen atmosphere. 171.6 g of HP 5540 and subsequently 105.7 g of GLYMO were metered in (pH after the addition = 2.0), heated to 65 ° C. and stirred for 1 hour. 5.88 g of formic acid (HCOOH = 85% by weight) was added and 44.45 g of Dynasylan® 1122 was metered through the metering device. An additional 0.98 g of formic acid (HCOOH = 85% by weight) had to be added to reach pH 3.8. Thereafter, the mixture was further stirred at 65 ° C. for 3 hours. Finally, at about 120 mbar, 159.4 g of alcohol / water mixture were removed by distillation. To the batch was added 24.57 g of water and 0.92 g of formic acid (HCOOH = 85% by weight). The residue cooled to room temperature was filtered through paint filter paper. The final mass of the residue was 661.44 g.
A milky turbid liquid having a pH value of 4.0 was obtained.
The product is shelf stable for at least 6 months.
Dry residue: 25.8% by weight
SiO ₂ content: 15.5% by mass
Free methanol: 1.1% by mass
Free ethanol: 0.5% by mass.

Example 15
In a 2 l stirrer equipped with a metering device and a reflux condenser, 1150.7 g of water and 2.0 g of formic acid (HCOOH = 85 mass%) were charged under a nitrogen atmosphere. 196 g of HP 1535 followed by 210 g of GLYMO (pH after the addition = 2.5) and heated to 65 ° C. and stirred for 1 hour. 11.73 g of formic acid (HCOOH = 85% by mass) was added, and 90 g of bis AMEO was metered in via the metering device. An additional 2.6 g of formic acid (HCOOH = 85% by weight) had to be added to reach pH 4.0. Thereafter, the mixture was further stirred at 65 ° C. for 3 hours. Finally, at about 230 mbar, 321.52 g of alcohol / water mixture was removed by distillation. To the batch were added 42.85 g of water and 1.0 g of formic acid (HCOOH = 85% by weight). The residue cooled to room temperature was filtered through paint filter paper. The final mass of the residue was 1329.12 g.
A milky liquid having a pH value of 4.3 was obtained.
The product is shelf stable for at least 6 months.
Dry residue: 20.7% by mass
SiO ₂ content: 10.7% by mass
Free methanol: 1.1% by mass
Free ethanol: 0.6% by mass.

Example 16
In a 2 l stirrer equipped with a metering device and a reflux condenser, 758.8 g of water and 2.13 g of formic acid (HCOOH = 85 mass%) were charged under a nitrogen atmosphere. 588 g of HP 1535 and subsequently 210 g of GLYMO were metered in (pH after the addition = 2.5), heated to 65 ° C. and stirred for 1 hour. 11.73 g of formic acid (HCOOH = 85% by weight) was added and 90 g of Dynasylan® 1122 was metered through the metering device. Thereafter, the mixture was further stirred at 65 ° C. for 3 hours. Finally, at about 300 mbar, 306.17 g of alcohol / water mixture were removed by distillation. To the batch was added 25.15 g of water. The residue cooled to room temperature was filtered through paint filter paper. The final mass of the residue was 1346.94 g.
A milky liquid having a pH value of 4.2 was obtained.
The product is shelf stable for at least 6 months.
Dry residue: 30.8% by mass
SiO ₂ content: 20.5% by mass
Free methanol: 1.3% by mass
Free ethanol: 0.6% by mass.

Example 17
In a 2 l stirrer equipped with a metering device and a reflux condenser, 831.9 g of water and 3.0 g of formic acid (HCOOH = 85% by mass) were charged under a nitrogen atmosphere. 514.5 g of HP 5540 and subsequently 210 g of GLYMO were metered in (pH after the addition = 2.0), heated to 65 ° C. and stirred for 1 hour. 11.74 g of formic acid (HCOOH = 85% by weight) was added and 90 g of Dynasylan® 1122 was metered through the metering device. A total of 1.77 g of formic acid (HCOOH = 85% by weight) had to be added to reach pH 4.0. Thereafter, the mixture was further stirred at 65 ° C. for 3 hours. Finally, at about 180 mbar, 314.63 g of alcohol / water mixture were removed by distillation. To the batch, 38.02 g of water was added. The residue cooled to room temperature was filtered through paint filter paper. The final mass of the residue was 1334.02 g.
A milky liquid having a pH value of 4.3 was obtained.
The product is shelf stable for at least 6 months.
Dry residue: 31.0% by mass
SiO ₂ content: 20.7% by mass
Free methanol: 1.1% by mass
Free ethanol: 0.5% by mass.

Example 18
In a 2 l stirrer equipped with a metering device and a reflux condenser, 1003.7 g of water and 3.0 g of formic acid (HCOOH = 85% by mass) were charged under a nitrogen atmosphere. 343 g of HP 5540 and subsequently 210 g of GLYMO were metered in (pH after the addition = 3.0), heated to 65 ° C. and stirred for 1 hour. 11.88 g of formic acid (HCOOH = 85% by mass) was added and 90 g of bis AMEO was metered in via the metering device. An additional 2.32 g of formic acid (HCOOH = 85% by weight) had to be added to reach pH 4.0. Thereafter, the mixture was further stirred at 65 ° C. for 3 hours. Finally, at approximately 200 mbar, 311.97 g of alcohol / water mixture was removed by distillation. To the batch, 28.71 g of water was added. The residue cooled to room temperature was filtered through paint filter paper. The final mass of the residue was 1343.39 g. A milky liquid having a pH value of 4.2 was obtained.
The product is shelf stable for at least 6 months.
Dry residue: 25.9% by weight
SiO ₂ content: 15.7% by mass
Free methanol: 1.1% by mass
Free ethanol: 0.5% by mass.

Example 19
In a 2 liter stirring apparatus equipped with a metering apparatus and a reflux condenser, 1175.1 g of water and 3.0 g of formic acid (HCOOH = 85 mass%) were charged under a nitrogen atmosphere. 171.5 g of HP 5540 followed by 210 g of GLYMO (pH after the addition = 2.0) were heated to 65 ° C. and stirred for 1 hour. 11.73 g of formic acid (HCOOH = 85% by mass) was added, and 90 g of bis AMEO was metered in via the metering device. An additional 0.91 g of formic acid (HCOOH = 85% by weight) had to be added to reach pH 4.0. Thereafter, the mixture was further stirred at 65 ° C. for 3 hours. Finally, at about 190 mbar, 336.96 g of alcohol / water mixture was removed by distillation. To the batch, 58.03 g of water was added. The residue cooled to room temperature was filtered through paint filter paper. The final mass of the residue was 1314.02 g.
A cloudy pale beige liquid having a pH value of 5.0 was obtained.
The product is shelf stable for at least 6 months.
Dry residue: 21.2% by mass
SiO ₂ content: 10.7% by mass
Free methanol: 0.9% by mass
Free ethanol: 0.5% by mass.

Example 20
In a 2 liter stirring device equipped with a metering device and a reflux condenser, 133.11 g of water and 2.07 g of formic acid (HCOOH = 85% by mass) were charged under a nitrogen atmosphere. 150 g of GLYMO was metered in, heated to 65 ° C. and stirred for 1 hour. 18.21 g of formic acid (HCOOH = 85% by weight) was added and 30 g of Dynasylan® A and 120 g of Dynasylan® 1122 were metered through the metering device. Thereafter, the mixture was further stirred at 65 ° C. for 3 hours. Finally, at about 140 mbar, 332.97 g of alcohol / water mixture were removed by distillation. To the batch was added 13.65 g of water. The residue cooled to room temperature was filtered through a Seitz T-950 filter sheet. The final mass of the residue was 1311.58 g.
A yellowish clear liquid having a pH value of 4.5 was obtained.
The product is shelf stable for at least 6 months.
Dry residue: 14.7% by mass
SiO ₂ content: 6.1% by mass
Free methanol: 1.3% by mass
Free ethanol: 1.1% by mass.

Example 21
In a 2 l stirrer equipped with a metering device and a reflux condenser, 1419.98 g of water and 2.04 g of formic acid (HCOOH = 85 mass%) were charged under a nitrogen atmosphere. 150 g of GLYMO was metered in, heated to 65 ° C. and stirred for 1 hour. 11.80 g of formic acid (HCOOH = 85% by weight) was added and 60 g of Dynasylan® A and 90 g of Dynasylan® 1122 were metered through the metering device. Thereafter, the mixture was further stirred at 65 ° C. for 3 hours. Finally, at about 150 mbar, 417.63 g of alcohol / water mixture were removed by distillation. To the batch, 81.99 g of water was added. The residue cooled to room temperature was filtered through a Seitz T-950 filter sheet. The final mass of the residue was 1306.34 g.
A yellowish clear liquid having a pH value of 4.5 was obtained.
The product is shelf stable for at least 6 months.
Dry residue: 13.4% by weight
SiO ₂ content: 5.8% by mass
Free methanol: 0.8% by mass
Free ethanol: 0.7% by mass.

Example 22
In a 2 l stirrer equipped with a metering device and a reflux condenser, 1525.36 g of water and 2.06 g of formic acid (HCOOH = 85% by mass) were charged under a nitrogen atmosphere. 180 g of GLYMO was metered in, heated to 65 ° C. and stirred for 1 hour. 15.00 g of formic acid (HCOOH = 85% by weight) was added and 15 g Si 264 and 105 g Dynasylan® 1122 and metered via the metering device. Thereafter, the mixture was further stirred at 65 ° C. for 3 hours. Finally, at about 130 mbar, 408.08 g of alcohol / water mixture were removed by distillation. To the batch was added 124.11 g of water. The residue cooled to room temperature was filtered through a Seitz T-950 filter sheet. The final mass of the residue was 1417.98 g.
A yellowish clear liquid having a pH value of 4.5 was obtained.
The product is shelf stable for at least 6 months.
Dry residue: 13.4% by weight
SiO ₂ content: 5.1% by mass
Free methanol: 0.9% by mass
Free ethanol: 0.5% by mass.

Example 23
In a 2 l stirrer equipped with a metering device and a reflux condenser, 1540.21 g of water and 2.06 g of formic acid (HCOOH = 85% by mass) were charged under a nitrogen atmosphere. 180 g of GLYMO was metered in, heated to 65 ° C. and stirred for 1 hour. 15.01 g of formic acid (HCOOH = 85% by weight) was added and 30 g of Dynasylan® 2201 and 105 g of Dynasylan® 1122 were metered through the metering device. Thereafter, the mixture was further stirred at 65 ° C. for 3 hours. Finally, at about 150 mbar, 424.56 g of alcohol / water mixture was removed by distillation. To the batch was added 123.63 g of water. The residue cooled to room temperature was filtered through a Seitz T-950 filter sheet. The final mass of the residue was 1433.42 g.
A yellowish liquid having a pH value of 4.5 was obtained.
The product is shelf stable for at least 6 months.
Dry residue: 13.5% by mass
SiO ₂ content: 5.1% by mass
Free methanol: 0.8% by mass
Free ethanol: 0.4% by mass.

Example 24
In a 2 l stirrer equipped with a metering device and a reflux condenser, 1525.28 g of water and 2.02 g of formic acid (HCOOH = 85% by mass) were charged under a nitrogen atmosphere. GLYMO 179.91 g was metered in, heated to 65 ° C. and stirred for 1 hour. 15.01 g of formic acid (HCOOH = 85% by weight) was added and 15.84 g of Dynasylan® MTMO and 105.23 g of DS 1127 were metered in via the metering device. Thereafter, the mixture was further stirred at 65 ° C. for 3 hours. Finally, at about 200 mbar, 335.83 g of alcohol / water mixture were removed by distillation. To the batch, 52.39 g of water was added. The residue cooled to room temperature was filtered through a Seitz T-950 filter sheet. The final mass of the residue was 1491.77 g.
A colorless clear liquid having a pH value of 4.5 was obtained.
The product is shelf stable for at least 6 months.
Dry residue: 13.5% by mass
SiO ₂ content: 5.1% by mass
Free methanol: 1.1% by mass
Free ethanol: 0.6% by mass.

Example 25
In a 2 l stirrer equipped with a metering device and a reflux condenser, 1525.68 g of water and 2.02 g of formic acid (HCOOH = 85% by mass) were charged under a nitrogen atmosphere. 180.15 g of GLYMO was metered in, heated to 65 ° C. and stirred for 1 hour. 15.01 g of formic acid (HCOOH = 85% by weight) was added and 29.98 g (1: 1) Si 264 in methanol and 105 g Dynasylan® 1122 were metered through the metering device. Thereafter, the mixture was further stirred at 65 ° C. for 3 hours. Finally, at about 130 mbar, 370.58 g of alcohol / water mixture was removed by distillation. To the batch, 67.71 g of water was added. The residue cooled to room temperature was filtered through a Seitz T-950 filter sheet. The final mass of the residue was 1474.32 g.
A colorless clear liquid having a pH value of 4.5 was obtained.
The product is shelf stable for at least 6 months.
Dry residue: 13.6% by mass
SiO ₂ content: 5.1% by mass
Free methanol: 1.3% by mass
Free ethanol: 0.6% by mass.

Example 26
In a 2 liter stirring apparatus equipped with a metering apparatus and a reflux condenser, 1203.89 g of water and 3.00 g of formic acid (HCOOH = 85% by mass) were charged under a nitrogen atmosphere. Subsequently, 135.68 g of Koestrosol 3550 was added all at once, and 180 g of Dynasylan® GLYMO was metered in via a metering device. The batch was heated to 65 ° C. and stirred at this temperature for 1 hour. 17.7 g of formic acid (HCOOH = 85% by weight) was added and 120 g of Dynasylan® 1122 was metered through the metering device. Thereafter, the mixture was further stirred at 65 ° C. for 3 hours, and 1.11 g of formic acid (HCOOH = 85% by mass) was additionally added. Finally, at about 180 mbar, 340.64 g of alcohol / water mixture was removed by distillation. To the batch was added 38.80 g of deionized water.
The final mass of the residue was 1347.82 g.
To the batch, 36.19 g of alcohol / water mixture was removed by distillation at a freshness of about 180 mbar and mixed with 51.22 g of deionized water. The cooled residue was filtered through a Seitz T-950 filter sheet.
The final mass of the residue was 1347.82 g.
An opalescent liquid having a pH value of about 4.3 was obtained.
The product is shelf stable for at least 6 months.
Dry residue: 20.6% by mass
SiO ₂ content: 10.8% by mass
Free methanol: 0.4% by mass
Free ethanol: 0.7% by mass.

Example 27
In a 2 l stirrer equipped with a metering device and a reflux condenser, 1067.61 g of water and 3.00 g of formic acid (HCOOH = 85 mass%) were charged under a nitrogen atmosphere. Subsequently, 271.09 g of Koestrosol 3550 was added all at once, and 180.16 g of GLYMO was metered in via a metering device. The batch was heated to 65 ° C. and stirred at this temperature for 1 hour.
After stirring at 65 ° C. for 1 hour, the batch was additionally adjusted to pH 3.0 with 2.79 g of formic acid (HCOOH = 85% by weight) and stirred again at 65 ° C. for 0.5 hour. Subsequently, 17.71 g of formic acid (HCOOH = 85% by weight) were added and 120.06 g of Dynasylan® 1122 were metered in. The batch was then further stirred at 65 ° C. for 3 hours and once again mixed with 3.21 g of formic acid (HCOOH = 85% by weight). Finally, at approximately 160 mbar, 343.80 g of alcohol / water mixture were removed by distillation.
To the batch was added 48.91 g of deionized water.
The cooled residue was filtered through a Seitz T-950 filter sheet.
The final mass of the residue was 1308.51 g.
An opalescent liquid having a pH value of about 4.0 was obtained.
The product is shelf stable for at least 6 months.
Dry residue: 26.0% by weight
SiO ₂ content: 15.8% by mass
Free methanol: 1.0% by mass
Free ethanol: 0.5% by mass.

Example 28
In a 2 l stirrer equipped with a metering device and a reflux condenser, 1203.54 g of water and 2.99 g of formic acid (HCOOH = 85% by mass) were charged under a nitrogen atmosphere. Subsequently, 135.59 g of Koestrosol 3550 was added all at once, and 165 g of GLYMO was metered in via a metering device. The batch was heated to 65 ° C. and stirred at this temperature for 2 hours.
Dry residue: 20.4% by mass
SiO ₂ content: 13.6% by mass
Free methanol: 1.2% by mass
Free ethanol: 0.5% by mass.

Example 29
In a 2 liter stirring apparatus equipped with a metering apparatus and a reflux condenser, 120.16 g of water and 3.00 g of formic acid (HCOOH = 85% by mass) were charged under a nitrogen atmosphere. Subsequently, 135.55 g of Koestrosol 3550 was added all at once, and 165 g of GLYMO was metered in via a metering device. The batch was heated to 65 ° C. and stirred at this temperature for 2 hours.
Dry residue: 20.5% by mass
SiO ₂ content: 11.0% by mass
Free methanol: 1.5% by mass
Free ethanol: 0.6% by mass.

Example 30
In a 2 l stirrer equipped with a metering device and a reflux condenser, 1112.88 g of water and 1.01 g of formic acid (HCOOH = 85% by mass) were charged under a nitrogen atmosphere. First, 225.49 g of Koestrosol K 1530 (pH after the addition = 3.5) and then 180 g of GLYMO were metered in, heated to 65 ° C. and stirred for 1 hour. Subsequently, 18.71 g of formic acid (HCOOH = 85% by mass) was added, and 120 g of bis AMEO was metered in via the metering device. Stir at 65 ° C. for 3 hours at a pH value of 4.0. Finally, at about 130 mbar, 321.56 g of alcohol / water mixture was removed by distillation. To the batch was added 20.23 g of water. The residue, cooled to room temperature (RT), was filtered through a Seitz T-950 filter sheet. The final mass of the residue was 1334.77 g.
A liquid having a pH value of 4.0 was obtained. The product is shelf stable for at least 6 months.
Dry residue: 20.9% by mass
SiO ₂ content: 10.5% by mass
Free methanol: 1.2% by mass
Free ethanol: 0.8% by mass.

Example 31
In a 2 l stirrer equipped with a metering device and a reflux condenser, 1220.56 g of water and 2.02 g of formic acid (HCOOH = 85% by mass) were charged under a nitrogen atmosphere. 180 g of GLYMO was metered in, heated to 65 ° C. and stirred for 1 hour. Subsequently, 15.00 g of formic acid (HCOOH = 85% by mass) was added, and 90 g of bis AMEO was metered in via the metering device. After 15 minutes, 30.0 g of PTMO was added. Stir at 65 ° C. for 3 hours at a pH value of 4.0. Finally, at about 130 mbar, 316.39 g of alcohol / water mixture were removed by distillation. To the batch was added 18.68 g of water. The residue cooled to RT was filtered through a Seitz T-950 filter sheet. The final mass of the residue was 1212.58 g.
A yellowish clear liquid having a pH value of 4.0 was obtained. The product is shelf stable for at least 6 months.
Dry residue: 16.9% by weight
SiO ₂ content: 6.7% by mass
Free methanol: 1.6% by mass
Free ethanol: 0.6% by mass.

Example 32
In a 2 l stirrer equipped with a metering device and a reflux condenser, 133.02 g of water and 1.98 g of formic acid (HCOOH = 85% by mass) were charged under a nitrogen atmosphere. 135.69 g of GLYMO was metered in (pH after the addition = 3.0), heated to 65 ° C. and stirred for 1 hour. Subsequently, 20.09 g of formic acid (HCOOH = 85% by mass) was added, and 120.01 g of bisAMEO was metered in via the metering device. After 15 minutes 44.96 g of PTMO was added. Stir at 65 ° C. for 3 hours at a pH value of 3.9. Finally, at about 130 mbar, 344.63 g of alcohol / water mixture were removed by distillation. To the batch, 45.51 g of water was added. The residue cooled to RT was filtered through a Seitz K-900 filter sheet. The final mass of the residue was 1340.46 g.
A yellowish clear liquid having a pH value of 3.9 was obtained. The product is shelf stable for at least 6 months.
Dry residue: 14.7% by mass
SiO ₂ content: 6.9% by mass
Free methanol: 1.0% by mass
Free ethanol: 0.6% by mass.

Example 33
Under a nitrogen atmosphere, 1324.50 g of water and 2.01 g of formic acid (HCOOH = 85% by mass) were charged in a 2 liter stirring device equipped with a metering device and a reflux condenser. 120.27 g of GLYMO was metered in (pH after the addition = 3.0), heated to 65 ° C. and stirred for 1 hour. Thereafter, 22.01 g of formic acid (HCOOH = 85% by mass) was added, and 119.75 g of bis AMEO was metered in via the metering device. After 15 minutes, 60.35 g of PTMO was added. Stir at 65 ° C. for 3 hours at a pH value of 3.9. Finally, at about 130 mbar, 314.81 g of alcohol / water mixture were removed by distillation. To the batch, 3.59 g of water was added. The residue cooled to RT was filtered through a Seitz K-900 filter sheet. The final mass of the residue was 1329.04 g.
A yellowish clear liquid having a pH value of 3.9 was obtained. The product is shelf stable for at least 6 months.
Dry residue: 14.8% by weight
SiO ₂ content: 6.0% by mass
Free methanol: 1.4% by mass
Free ethanol: 0.8% by mass.

Example 34
In a 2 l stirrer equipped with a metering device and a reflux condenser, 1265.70 g of water and 3.05 g of formic acid (HCOOH = 85% by mass) were charged under a nitrogen atmosphere. First, 133.43 g of Koestrosol 3550 (pH after the addition = 3.0) and then 134.93 g of GLYMO were metered in, heated to 65 ° C. and stirred for 1 hour. 21.08 g of formic acid (HCOOH = 85% by mass) was added and 119.97 g of bis AMEO was metered in via the metering device. After stirring for 15 minutes, 44.99 g of PTMO was added. Stir at 65 ° C. for 3 hours at a pH value of 3.9. Finally, at about 130 mbar, 370.09 g of alcohol / water mixture was removed by distillation. To the batch was added 32.57 g of water. The residue cooled to RT was filtered through a Seitz K-900 filter sheet. The final mass of the residue was 1340.09 g.
A milky liquid having a pH value of 3.9 was obtained. The product is shelf stable for at least 6 months.
Dry residue: 19.8% by weight
SiO ₂ content: 11.0% by mass
Free methanol: 1.3% by mass
Free ethanol: 1.1% by mass.

Example 35
In a 2 l stirrer equipped with a metering device and a reflux condenser, 1275.04 g of water and 1.96 g of formic acid (HCOOH = 85% by mass) were charged under a nitrogen atmosphere. 120.23 g of GLYMO was metered in (pH after the addition = 3.0), heated to 65 ° C. and stirred for 1 hour. 18.03 g of formic acid (HCOOH = 85% by weight) are added, and 30.12 g of Dynasylan® A are first added via the metering device and stirred until a slightly cloudy batch is clear. . Then 119.98 g of bis AMEO was metered in. After 15 minutes, 30.08 g of PTMO was added. Stir at 65 ° C. for 3 hours at a pH of 3.9. Finally, at about 130 mbar, 340.64 g of alcohol / water mixture was removed by distillation. The residue cooled to RT was filtered through a Seitz K-900 filter sheet. The final mass of the residue was 1259.89 g.
A yellowish clear liquid having a pH value of 3.9 was obtained. The product is shelf stable for at least 6 months.
Dry residue: 17.4% by weight (in order to carry out the use test, the product was diluted with deionized water to a solids content of 15% by weight)
SiO ₂ content: 6.2% by mass
Free methanol: 1.2% by mass
Free ethanol: 1.2% by mass.

Testing the stability of aqueous binders in the alkaline region.

Example of use Cleaning of DC01 C290, 152 × 76 × 0.8 mm test steel plate R-36 (Rocholl) The test steel plate was cleaned with an organic solvent (ethyl acetate) and subsequently placed in an alkaline cleaning bath (composition: S 5610 ( Chemetall) 10.0 g / l, pH 11.5, 60 ° C., 35 seconds). After the alkali cleaning, the metal substrate was rinsed with deionized water. Excess water was blown off the surface with a compressed air gun.

2. Corrosion investigation The corrosion test (abbreviated as NSS) was carried out in salt spray (test according to DIN 50021-SS).
The crosscut test was carried out according to EN ISO 2409.

3. Additives used in this use example: Zinc dust "superfine" 3 Micron (Numinor) (zinc powder)
・ MIOX MICRO 30 (Kaerntner Montanindustrie) (natural mica-like iron oxide)
Bayferrox Rot 130 BM (Harald-Scholz Co. & GmbH) (organic colorant with Fe ₂ O ₃ )
・ Zinc Oxide Red Seal (NUMINOR)
Sikron M500 (SIBELCO, Benelux) (crystalline silica powder, SiO ₂ powder).

4). Binders used in the comparative use examples For the use examples, the following binders were used:

5. Additives B and C were added and produced in a Hauschild universal mixer, mechanical type AM 501 T

  Additives B and C were produced in a universal mixing device (Hauschild machine type AM 501 T). Additive mixtures B and C were mixed in a universal mixer at 3 × 30 seconds at 3000 rpm, respectively.

6). Production of the composition for the use case to be compared was carried out in a universal mixing device (Hauschild machine type AM 501 T) in the binder at 3 000 rpm for 3 × 20 seconds each at 3000 rpm. See Tables 1 and 2, dispersed in

Table 1:
Prepared composition for comparative example (the pH value of the composition was measured 30 minutes after each preparation):

Table 2:
Composition produced for use according to the invention (the pH value of the composition was measured 30 minutes after each preparation):

7). Coating of the washed test steel sheet 1. On the prepared test steel sheet, the composition or composition produced according to Tables 1 and 2 was used with a film applicator at a wet film thickness of 80 μm. And applied.

  After the coating, the plate was dried at 20 ° C. for 24 hours and scratched.

  The adhesion of the coated substrate was tested using a cross cut test.

Result “cross cut” after curing for 24 hours at 20 ° C. (EN ISO 2409)
Comparative Example 1: 1
Comparative Example 2: 1
Usage example 1: 1
Comparative Example 3: 0
Comparative Example 4: 1
Use case 2: 1
Comparative Example 5: 2
Use Case 3: 0
Use Example 4: 1.

  Furthermore, the coated and scratched substrates were tested and evaluated for corrosion resistance in salt spray (DIN 50021-SS).

Results after a 26 hour salt spray test (see also Table 3):
Comparative Example 1: Corrosion on Scratch (Ritz) and partially on the surface Comparative Example 2: Roughly no corrosion Use Example 1: Roughly no corrosion Comparative Example 3: Corrosion on and on scratch Comparative Example 4: Corrosion Peeling of the accompanying coating Use example 2: Almost no corrosion.

Results after 150 hours of salt spray (see also Table 3):
Comparative Example 5: Corrosion on scratch and partially on surface Use Example 3: No corrosion on scratch and surface Use Example 4: Corrosion on scratch and partially on surface

Samples from Use Example 3 were coated with a two-part epoxy resin: Standox, EP Primer Surfacer and Standox EP Curing Agent. Mixing ratio 2: 1 (as specified). The coating system was applied with a doctor blade (wet film thickness 80 μm, dry film thickness approximately 30 μm) and cured at 20 ° C. for 24 hours. A comparative sample (simply washed thin steel plate) was similarly coated.
Crosscut Sample 1 (Use Example 3 + Epoxy resin coating): 0
Cross-cut sample 2 (thin steel plate + epoxy resin coating): 0
Both samples were scratched with 1 mm scratches and examined for corrosion in a salt spray. After 200 h, Sample 2 showed severe corrosion and peeling on the scratch, while Sample 1 was not corroded on the scratch.

  The results from the usage survey are summarized once again in Table 3 below, because unfortunately it is still not possible to reproduce the corresponding suitable figure in the patent specification.

Table 3:
List of results from technical survey before and after salt spray test

In summary, you can see that:
Comparative Examples 1 and 2 after 26 hours in salt spray and Use Example 1:
Comparative Example 1 shows corrosion on the scratch and partially on the surface already after 26 hours. On the other hand, Comparative Example 2 and Comparative Example 1 do not have corrosion on the scratch.

Comparative examples 3 and 4 and use example 2 after 26 hours in salt spray:
Comparative Example 3 shows corrosion on the scratch and on the surface after 26 hours in the salt spray, while Comparative Example 4 used has only some corrosion on the scratch, but observes some peeling. be able to. Use Example 2 shows the best results. This cannot confirm corrosion on the scratch.

Comparative Example 5 and Use Examples 3 and 4 after 150 hours in salt spray:
Comparative Example 5 and Use Example 4 show corrosion on scratch after 150 hours in salt spray, whereas Use Example 3 is completely free of corrosion on scratch after 150 hours.
Use Example 5 shows no corrosion on the scratch after 28, 90 and 150 hours. However, a slight discoloration can be observed on the surface.

  Use Example 6 shows no corrosion on the scratch after 17 hours, partial corrosion on the scratch after 150 hours and almost continuous corrosion on the scratch after 250 hours. But the surface is without corrosion.

  Use Example 7 shows no corrosion on the scratch after 19 hours in salt spray. However, after 135 hours, continuous corrosion on the scratch can be confirmed.

Claims (15)

A composition comprising:
Formula I
_{^{X-Si (R 2) x}} (OR 1) 3-x (I)
[Wherein, X represents a 2- (3,4-epoxycyclohexyl) ethyl group, a 1-glycidyloxymethyl group, a 2-glycidyloxyethyl group, a 3-glycidyloxypropyl group or a 3-glycidyloxyisobutyl group, R ^{1 and} R ² are each independently a linear or branched alkyl group having 1 to 4 carbon atoms, and x is equal to 0 or 1.]-Glycidyloxyalkylalkoxy Silane,
Formula II
(OR ¹ ) ₃ Si-A-Si (OR ¹ ) ₃ (II)
In which the radicals R ¹ are the same or different and R ¹ is a linear or branched alkyl group having 1 to 4 carbon atoms, and A is of the formula IIa
_{- (CH 2) i - [} NH (CH 2) f] g NH [(CH 2) f * NH] g * - (CH 2) i * - (IIa)
Represents a bisamino functional group represented by
Here, i, i *, f, f *, g or g * are the same or different, i and / or i * = 1, 2, 3 or 4, f and / or f * = 1 or 2, g And / or at least one bis (alkoxysilylalkyl) amine represented by g * = 0 or 1],
Optionally, at least one further from among tetraalkoxysilane, alkylalkoxysilane, mercaptoalkylalkoxysilane, carboxyalkylalkoxysilane, aminoalkylalkoxysilane, ureidoalkylalkoxysilane, thiocyanatoalkylalkoxysilane and silica sol. A binder containing at least one cocondensate based on a silicon compound;
·water,
An alcohol in an amount of less than 3% by weight, based on the composition
Including at least one additive and optionally at least one additive from among particulate metals, metal alloys and / or metal compounds,
In that case, the composition has a pH value of 1 to 14 in the composition, and the dry residue of the binder is 1 to 50% by mass based on the binder used. In order to produce the binder,
Based on the silane used according to formulas I, II and optionally the silicon compound mentioned above, a molar excess of water is charged, adjusted to an acidic pH value with the addition of organic or inorganic acids, and optionally At that time, add silica sol,
Metering and heating an ω-glycidyloxyalkylalkoxysilane of formula I;
Optionally, after metering acid,
And at least one bis (alkoxysilylalkyl) amine of the general formula II and optionally tetraalkoxysilane, alkylalkoxysilane, mercaptoalkylalkoxysilane, carboxyalkylalkoxysilane, aminoalkylalkoxysilane, ureidoalkylalkoxysilane and thiocyana Metering and reacting at least one further silicon compound from among the toalkylalkoxysilanes;
Subsequently, the hydrolyzed alcohol produced thereby is at least partially removed from the reaction mixture under reduced pressure,
The binder thus obtained is optionally diluted with water and / or an aqueous acid solution and subsequently filtered,
In that case, the dry residue of the binder is 1 to 50% by weight, preferably 5 to 40% by weight, particularly preferably 8 to 35% by weight, in particular 10 to 25% by weight, based on the binder used. The composition of claim 1, wherein   The composition according to claim 1 or 2, which is a dry residue (solid content) of 1 to 50% by weight, preferably 3 to 45% by weight, particularly preferably 3 to 35% by weight, based on the composition.   The content of the particulate metal, metal alloy and / or metal compound in the composition is from 1 to 95% by weight, preferably from 3 to 90% by weight, particularly preferably from 5 to 85% by weight, very particularly preferably from 10 to 80%. The composition according to any one of claims 1 to 3, wherein the composition is% by mass.   The additive of granular metal, metal alloy and / or metal compound, especially metal oxide, is made of conductive or non-conductive filler, zinc powder, zinc lamella, zinc powder, zinc alloy, zinc bismuth alloy Powder or lamella or fine powder, aluminum powder, aluminum lamella, powder or lamella or powder made of aluminum alloy, magnesium powder, magnesium lamella, powder or lamella made of magnesium alloy, titanium dioxide, red iron oxide, yellow iron oxide, calcium carbonate, Talc, aluminum silicate, barium sulfate, kaolin, magnesium silicate, crystalline quartz, amorphous quartz, calcium carbonate, calcium silicate, aluminum oxide, zeolite, wollastonite, zinc oxide, zinc phosphate, vanadic acid Bismuth, lead chromate, silicon carbide and inorganic colors Any one composition according is selected from claims 1 to 4 out of the fee.   The additive is used in antifoaming agents, thickeners, rheology aids, dispersion aids, antisettling agents, rust inhibitors, wetting agents, organic pigments, polymers or polymer dispersions and catalysts for the condensation and curing. The composition according to any one of claims 1 to 5, wherein the composition is selected from:   Additives, in particular 0 to 5% by weight thickener and / or 0 to 5% by weight anti-settling agent and / or 0 to 3% by weight wetting agent and / or 0 to 1, respectively, based on the composition The composition according to any one of claims 1 to 6, wherein the composition has a content of mass% of a corrosion inhibitor, and the total of all components present in the composition is 100% by mass. It is a manufacturing method of the composition of any one of Claim 1-7, Comprising:
First of all, the formula I
_{^{X-Si (R 2) x}} (OR 1) 3-x (I)
[Wherein, X represents a 2- (3,4-epoxycyclohexyl) ethyl group, a 1-glycidyloxymethyl group, a 2-glycidyloxyethyl group, a 3-glycidyloxypropyl group or a 3-glycidyloxyisobutyl group, R ^{1 and} R ² are each independently a linear or branched alkyl group having 1 to 4 carbon atoms, and x is equal to 0 or 1.]-Glycidyloxyalkylalkoxy Silane,
Formula II
(OR ¹ ) ₃ Si-A-Si (OR ¹ ) ₃ (II)
In which the radicals R ¹ are the same or different and R ¹ is a linear or branched alkyl group having 1 to 4 carbon atoms, and A is of the formula IIa
_{- (CH 2) i - [} NH (CH 2) f] g NH [(CH 2) f * NH] g * - (CH 2) i * - (IIa)
Represents a bisamino functional group represented by
Here, i, i ^* , f, f ^* , g or g ^* are the same or different, i and / or i ^* = 1, 2, 3 or 4, f and / or f ^* = 1 or 2, g And / or g ^* = 0 or 1], and at least one bis (alkoxysilylalkyl) amine,
Optionally, at least one further from among tetraalkoxysilane, alkylalkoxysilane, mercaptoalkylalkoxysilane, carboxyalkylalkoxysilane, aminoalkylalkoxysilane, ureidoalkylalkoxysilane, thiocyanatoalkylalkoxysilane and silica sol. A binder containing at least one cocondensate based on a silicon compound,
Charging a molar excess of water, based on the silane used according to formula I, II and optionally on said silicon compound,
Adjust to an acidic pH value with the addition of organic or inorganic acids, and optionally add silica sol with stirring,
Metering and heating an ω-glycidyloxyalkylalkoxysilane of formula I;
Optionally, after metering acid,
And at least one bis (alkoxysilylalkyl) amine of the general formula II and optionally tetraalkoxysilane, alkylalkoxysilane, mercaptoalkylalkoxysilane, carboxyalkylalkoxysilane, aminoalkylalkoxysilane, ureidoalkylalkoxysilane and isocyanate Metering and reacting at least one further silicon compound from among the natoalkylalkoxysilanes;
Subsequently, the hydrolyzed alcohol produced thereby is at least partially removed from the reaction mixture under reduced pressure,
The binder thus obtained is optionally diluted with water and / or aqueous acid and / or aqueous bases, or the pH value is adjusted and subsequently filtered,
And in the binder thus obtained, at least one additive from the particulate metal, metal alloy and / or metal compound is dispersed, and optionally at least one additive is mixed with stirring, and optionally The method for producing a composition according to any one of claims 1 to 7, wherein the composition is produced by adjusting a pH value in the composition.   The ω-glycidyloxyalkylalkoxysilane of the formula I is used in a molar ratio of 0.1 to 99.9 to 99: 1 with respect to the bis (alkoxysilylalkyl) amine of the general formula II, in particular the ω-glycidyloxyalkylalkoxy Silane is used in the binder in an amount of 0.001 to 42 mol%, preferably 0.01 to 30 mol%, particularly preferably 0.1 to 15 mol%, very particularly preferably 0.2 to 1.5 mol%. The method according to claim 8.   Based on the silane used according to formulas I and II and optionally the silicon compound mentioned above, a molar excess of water is preferably 2 per mole of alkoxy groups bonded to the Si in which the silane used is present. 9.-1000 mol of water, preferably 5-500 mol, in particular 10-100 mol of water are charged under protective gas, in which case the reaction is preferably carried out under nitrogen or argon. 9. The method according to 9.   The organic acid or inorganic acid is selected from formic acid, acetic acid, propionic acid, hydrochloric acid, nitric acid, sulfuric acid, phosphoric acid, and the aqueous base solution is caustic soda, caustic potash, N, N-dimethylethanolamine, tetrakis (Triethanolamine) zirconate and the pH value is 1 to 14, preferably after reaction in the binder and / or after the reaction and / or after compounding in the composition 2 to 12, particularly preferably 2.5 to 9, very particularly preferably 3 to 8, in particular 3.5; 4; 4.5; 5; 5.5; 6; 6.5; 7; 7. 5; 8 and 8.5, wherein the addition of the particulate metal, metal alloy and / or metal compound to the binder is also preferably micaceous iron oxide, zinc to the binder adjusted to acidity Addition of zinc oxide or zinc alloy During the method of the may lead to changes in the pH value, any one of claims 8 to 10.   As ω-glycidyloxyalkylalkoxysilane of the formula I, 3-glycidyloxypropyltrimethoxysilane and / or 3-glycidyloxypropyltriethoxysilane are used or metered, and the resulting acidic aqueous mixture is reduced to 0. 12. Heating to a temperature of 50 to 90 ° C., preferably 60 to 65 ° C. with stirring or mixing for 1 to 3 hours, preferably 0.5 to 2 hours. the method of. Tetraalkoxysilane, which contains ω-glycidyloxyalkylalkoxysilane and in the heated acidic mixture, as bis (trimethoxysilylpropyl) amine and / or bis (triethoxysilylpropyl) amine and optionally further silicon compounds, preferably tetramethoxysilane, tetraethoxysilane, alkylalkoxysilane, preferably C ₁ -C ₁₆ - alkyl alkoxy silanes, particularly methyltrimethoxysilane, methyltriethoxysilane, n- propyltrimethoxysilane (PTMO), n- propyl Triethoxysilane (PTEO), Isobutyltrimethoxysilane (IBTMO), Isobutyltriethoxysilane (IBTEO), Octyltrimethoxysilane (OCTMO), Octyltriethoxysilane (OCTE) ), Mercaptoalkylalkoxysilane, preferably 3-mercaptopropyltrimethoxysilane (MTMO), mercaptopropyltrimethoxysilane (MTEO), aminoalkylalkoxysilane, preferably 3-aminopropyltrimethoxysilane (AMMO), 3-amino Propyltriethoxysilane (AMEO), N- (2-aminoethyl) -3-aminopropyltrimethoxysilane (DAMO), N- (2-aminoethyl) -3-aminopropyltriethoxysilane, N, N'- Diaminoethyl-3-aminopropyltrimethoxysilane (TriAMO), N, N'-diaminoethyl-3-aminopropyltriethoxysilane, carboxyalkyltrialkoxysilane, ureidoalkylalkoxysilane, preferably -Ureidopropyltrimethoxysilane, 3-ureidopropyltriethoxysilane, and / or thiocyanatoalkylalkoxysilane, preferably 3-thiocyanatopropyltrimethoxysilane, 3-thiocyanatopropyltrimethoxysilane, 6, preferably at a pH value of 3-5, reacted with stirring at 50-90 ° C., preferably 60-65 ° C., for 0.3-6 hours, preferably 1-4 hours, ie use 13. A process according to any one of claims 8 to 12, wherein the alkoxysilane to be obtained is essentially completely hydrolyzed and condensed or cocondensed.   A composition according to any one of claims 1 to 7 or produced by a method according to any one of claims 8 to 13 for a coating which cures in air at a temperature of 16 to 26 ° C. Use of things.   Use according to claim 14, for coatings to protect metals and metal alloys from corrosion.